Evolution of oxygen-ion and proton conductivity in Ca-Doped Ln2Zr2O7 (Ln = Sm, Gd), located near pyrochlore fluorite phase boundary

• Autor(a) principal: Shlyakhtina, A. V.
• Data de Publicação: 2019
• Outros Autores: Abrantes, João, Gomes, Eduarda, Lyskov, N. V., Konysheva, E. Yu., Chernyak, S. A., Kharitonova, E. P., Karyagina, O. K, Kolbanev, I. V., Shcherbakova, L. G.
• Tipo de documento: Artigo
• Idioma: eng
• Título da fonte: Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
• Texto Completo: http://hdl.handle.net/20.500.11960/3059
• topic: Pyrochlore; Pyrochlore–fluorite morphotropic phase region; Proton conductivity; Oxygen—ion conductivity; Grain-boundary conductivity; Thermogravimetry; Rietveld refinement

Sm2-xCaxZr2O7-x/2 (x = 0, 0.05, 0.1) and Gd2-xCaxZr2O7-x/2 (x = 0.05, 0.1) mixed oxides in a pyrochlore-fluorite morphotropic phase region were prepared via the mechanical activation of oxide mixtures, followed by annealing at 1600 °C. The structure of the solid solutions was studied by X-ray diffraction and refined by the Rietveld method, water content was determined by thermogravimetry (TG), their bulk and grain-boundary conductivity was determined by impedance spectroscopy in dry and wet air (100-900 °C), and their total conductivity was measured as a function of oxygen partial pressure in the temperature range: 700-950 °C. The Sm2-xCaxZr2O7-x/2 (x = 0.05, 0.1) pyrochlore solid solutions, lying near the morphotropic phase boundary, have proton conductivity contribution both in the grain bulk and on grain boundaries below 600 °C, and pure oxygen-ion conductivity above 700 °C. The 500 °C proton conductivity contribution of Sm2-xCaxZr2O7-x/2 (x = 0.05, 0.1) is ~ 1 × 10-4 S/cm. The fluorite-like Gd2-xCaxZr2O7-x/2 (x = 0.1) solid solution has oxygen-ion bulk conductivity in entire temperature range studied, whereas proton transport contributes to its grain-boundary conductivity below 700 °C. As a result, of the morphotropic phase transition from pyrochlore Sm2-xCaxZr2O7-x/2 (x = 0.05, 0.1) to fluorite-like Gd2-xCaxZr2O7-x/2 (x = 0.05, 0.1), the bulk proton conductivity disappears and oxygen-ion conductivity decreases. The loss of bulk proton conductivity of Gd2-xCaxZr2O7-x/2 (x = 0.05, 0.1) can be associated with the fluorite structure formation. It is important to note that the degree of Ca substitution in such solid solutions (Ln2-xCax)Zr2O7-σ (Ln = Sm, Gd) is low, x < 0.1. In both series, grain-boundary conductivity usually exceeds bulk conductivity. The high grain-boundary proton conductivity of Ln2-xCaxZr2O7-x/2 (Ln = Sm, Gd; x = 0.1) is attributable to the formation of an intergranular CaZrO3-based cubic perovskite phase doped with Sm or Gd in Zr sublattice. © 2019 by the authors.